CA1218385A - Process for hydroxylating short-chain aliphatic mono- or di-olefins - Google Patents
Process for hydroxylating short-chain aliphatic mono- or di-olefinsInfo
- Publication number
- CA1218385A CA1218385A CA000360664A CA360664A CA1218385A CA 1218385 A CA1218385 A CA 1218385A CA 000360664 A CA000360664 A CA 000360664A CA 360664 A CA360664 A CA 360664A CA 1218385 A CA1218385 A CA 1218385A
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- olefin
- butene
- hydrogen peroxide
- double bond
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Glass Compositions (AREA)
- Iron Core Of Rotating Electric Machines (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A compound selected from 3-chloro-2-methyl-propene-1, straight-chain or branched monoolefins, which are either unsub-stituted or substituted by 1 to 2 hydroxyl groups and contain 4 to 7 carbon atoms and have a terminal or internal double bond, straight-chain or branched monoolefins, which are unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 8 to 12 carbon atoms and an internal double bond and straight-chain or branched diolefins containing 4 to 10 carbon atoms are reacted at a temperature between 30 and 80°C with less than 2 moles of formic acid and less than 2 moles of hydrogen peroxide per mole of double bond to be hydroxylated. Formic acid is used in a concentration between 20 and 50 percent by weight and hydrogen peroxide in a concentration of less than 50 percent by weight.
The concentration of the hydrogen peroxide in the aqueous phase of the reaction mixture is kept below 15 percent by weight during the entire reaction. From the monoolefins the corresponding diols and polyols are obtained directly in high yields within acceptable reaction times.
A compound selected from 3-chloro-2-methyl-propene-1, straight-chain or branched monoolefins, which are either unsub-stituted or substituted by 1 to 2 hydroxyl groups and contain 4 to 7 carbon atoms and have a terminal or internal double bond, straight-chain or branched monoolefins, which are unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 8 to 12 carbon atoms and an internal double bond and straight-chain or branched diolefins containing 4 to 10 carbon atoms are reacted at a temperature between 30 and 80°C with less than 2 moles of formic acid and less than 2 moles of hydrogen peroxide per mole of double bond to be hydroxylated. Formic acid is used in a concentration between 20 and 50 percent by weight and hydrogen peroxide in a concentration of less than 50 percent by weight.
The concentration of the hydrogen peroxide in the aqueous phase of the reaction mixture is kept below 15 percent by weight during the entire reaction. From the monoolefins the corresponding diols and polyols are obtained directly in high yields within acceptable reaction times.
Description
3`~
The present invention relates to a process for hydroxy-lating 3-chloro-2-methyl-propene-1, straight-chain or branched monoolefins, wllich are either unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 4 to 7 carbon atoms and a terminal or internal double bond, straight-chain or branched monoolefins, which are either unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 8 to 10 carbon atoms and an internal double bond, or straignt-chain or branched diolefins containing 4 to 10 carbon atoms.
By hydroxyldtion is meant that two hydroxyl groups are added on to the olefinic double bonds. Vicinal diols are thus formed in the hydroxylation of the monoolefins. If one or two hydroxyl groups are already present, then the corresponding triols or tetrols are formed. Unsaturated diols or saturated tetrols are formed in the hydroxylation of the diolefins.
The process according to the invention is characterized in that the olefin to be hydroxylated is reacted at a temperature between 30 and 80C with less than 2 moles of formic acid and less than 2 moles of hydrogen peroxide per mole of double bond to be hydroxylated, that formic acid is used in a concentration between 20 and 100 percent-and hydrogen peroxide in a concentra-tion of less than 50 percent by weight and that the concentration of the hydrogen peroxide in the aqueous phase of the reaction mixture is kept below 15 percent during the entire reaction.
The reaction is preferably carried out at a temperature between 45 and 60C. The formic acid is preferably used in an amount of 0.2 to 0.8 mole per mole of double bond to be hydroxy-lated. The hydrogen peroxide is used with advantage in an amount of 1.1 to 1.5 moles per mole of double bond to be hydroxylated.
Hydrogen peroxide having a concentration of 15 to 40 percent by weight is preferably used.
The starting materials used for the process according 3~`~
to the invention are 3-chloro-methyl-propene-1 straight-chain monoolefins containing 4 to 7 carbon atoms, such as butene-l, butene-2, pentene-l, hexene-l, heptene 1 and heptene-3 and branched-chain monoolefins containing 4 to 7 carbon atoms, such as 2-methyl-propene-1, 3-methyl-butene-1, 3,3-dimethyl-butene-1,
The present invention relates to a process for hydroxy-lating 3-chloro-2-methyl-propene-1, straight-chain or branched monoolefins, wllich are either unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 4 to 7 carbon atoms and a terminal or internal double bond, straight-chain or branched monoolefins, which are either unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 8 to 10 carbon atoms and an internal double bond, or straignt-chain or branched diolefins containing 4 to 10 carbon atoms.
By hydroxyldtion is meant that two hydroxyl groups are added on to the olefinic double bonds. Vicinal diols are thus formed in the hydroxylation of the monoolefins. If one or two hydroxyl groups are already present, then the corresponding triols or tetrols are formed. Unsaturated diols or saturated tetrols are formed in the hydroxylation of the diolefins.
The process according to the invention is characterized in that the olefin to be hydroxylated is reacted at a temperature between 30 and 80C with less than 2 moles of formic acid and less than 2 moles of hydrogen peroxide per mole of double bond to be hydroxylated, that formic acid is used in a concentration between 20 and 100 percent-and hydrogen peroxide in a concentra-tion of less than 50 percent by weight and that the concentration of the hydrogen peroxide in the aqueous phase of the reaction mixture is kept below 15 percent during the entire reaction.
The reaction is preferably carried out at a temperature between 45 and 60C. The formic acid is preferably used in an amount of 0.2 to 0.8 mole per mole of double bond to be hydroxy-lated. The hydrogen peroxide is used with advantage in an amount of 1.1 to 1.5 moles per mole of double bond to be hydroxylated.
Hydrogen peroxide having a concentration of 15 to 40 percent by weight is preferably used.
The starting materials used for the process according 3~`~
to the invention are 3-chloro-methyl-propene-1 straight-chain monoolefins containing 4 to 7 carbon atoms, such as butene-l, butene-2, pentene-l, hexene-l, heptene 1 and heptene-3 and branched-chain monoolefins containing 4 to 7 carbon atoms, such as 2-methyl-propene-1, 3-methyl-butene-1, 3,3-dimethyl-butene-1,
2,3-dimethylbutene-1, 2,3-dimethyl-butene-2, 2-methyl pentene-l, 2-methyl pentene-2, 3-methyl pentene-2 and 2-ethyl butene-l.
The monoolefins used can aiready have been substitu-ted by 1 to 2 hydroxyl groups. Examples of these substances are buten-1-ol-3, buten-2-ol-1 (crotyl alcohol), butene-2--diol-1,4, 3-methyl buten-
The monoolefins used can aiready have been substitu-ted by 1 to 2 hydroxyl groups. Examples of these substances are buten-1-ol-3, buten-2-ol-1 (crotyl alcohol), butene-2--diol-1,4, 3-methyl buten-
3-ol-1, 3-methyl buten-2-ol-1 and 2-methyl-buten-3-ol-2. While in the monoolefins con-taining a maximum of 7 carbon atoms the double bond can be in any position, thus at the chain end or internally in the chain, mono-olefins containing 8 to 10 carbon atoms can be reac~ed by means of the process according to the invention only if the double bond is internally in the chain.
Examples of these substances are 2,4,4-trimethyl pentene-2, 1,2-di-(tert. butyl)-ethylene and decene-5. The monoolefins containirg 8 to 10 carbon atoms can also be substituted by 1 to 2 hydroxyl groups as in 2-ethyl hexen-2-ol-1. Finally according to the process of the invention straight-chain or branched diolefins containing 4 to 10 carbon atoms such as butadiene, isoprene, hexadiene-1,5 and decadiene-l,9 can be reacted to the corresponding tetrols.
The process according to the invention is preferably carried out at standard pressure. ~owever, since the reaction temperature should not be lower than 30C in order to obtain an acceptable rate of reaction, it is obvious that for olefins having a boiling point lower than 30C, the use of excess pressure is required. In this case it is expedient to so select the reac-tion temperature that the pressure does not exceed 10 bars.
Despite the mild reaction conditions the reactions according to the process of the invention surprisingly are very smooth and result in high yields of the desired diols, triols or -tetrols within reasonable reaction times.
~ hen carrying out the reaction in practice preferably the entire formic acid to be used is used together with the olefin as the starting material and the hydroyen peroxide is slowly added portionwise. However, it is also possible to start with a portion, for example, approximately one third of the total amount of the olefin to be hydroxylated, together wlth the total amount of formic acid and to add slowly, portionwise -the hydro-gen peroxide and the residual amount of the olefin to be hydroxy-Iated. The reaction mixture is stirred intensively. An adequate post-reaction time after combining all the reactants in the reactor is recommended in order to improve the reaction rate.
After the reaction has been completed the reaction products usually are present in the aqueous yhase in -the dissolved form. For many purposes these aqueous solutions can be further used directly. However, noi only has the residual content of hydrogen peroxide an adverse effect in most cases but it is also desirable to isolate, in a purer form, the diols, triols or tetrols obtained. Various measures are then suitable for the further treatment.
If a second phase separates from the reaction mixture, then a phase separation can be carried out. In many cases it is then advisable to decompose, to a grea-t extent, the hydrogen peroxide, which is contained substantially only in the aqueous phase. The decomposition can be brought about by allowing the mixture to stand for a lengthy period at elevated temperature (digestion) or by the action of a suitable catalyst (for example by passing over a supported platinum fixed bed catalyst) or by a combination of these two measures.
The reaction mixture then is expediently neutralized 3~
and extracted with a suitable solvent, for example, ethyl acetate. The solvent is distilled from the extract and, if required, the residue of crude diol, -triol or tetrol is freed from water still contained therein by heating under reduced pressure. As an alternative, the neutralization of the formic acid contained in the reaction mixture can be dispensed with.
In that case it is expedient either to carry out the thickening operation continuously in the manner of a distillation with steam and to continue it until the distillate contains only small amounts of formic acid or the formic acid is separated discon-tinuously in sucll a way that after separating the bulk of formic acid the residue is once more mixed with water, thickened again, repeating this operation several times. The residue of crude diol, triol or tetrol can then be freed from the volatile com-ponents still contained therein by heating under reduced pressure.
The crude diols, triols or tetrols thus obtained have degrees of purity of approximately 88 to 96%. If ~urther purifica-tion is required, then this can be carried out in the usual manner by recrystallization or by fractional distillation under reduced pressure.
The process according to the invention will be further described with reference to the following Examples in which, unless otherwise stated, data in percent relate to percent by weight in all the cases.
Example 1 1 mole (72 g) of crotyl alcohol was mixed with 0.5 mole (23 g) of a 98% formic acid and 1.5 moles (340 g) of a 15%
H2O2 in a stirring apparatus, with a reflux condenser mounted thereon, and stirred for 8 hours at 60C. The system was single-phase and contained 3.9% of H2O2. The mix-ture was passed over an NW 40 column of 30 cm length. The column was filled with 100 ml of fixed-bed catalyst (0.1% of platinum on Berl saddles).
3~
After passing through H2O2 could no longer be detected analyti-cally.
The mixture was then boiled for 2 hours with reflux and concentrated in vacuo (bottom temperature up to 100C at 12 torrs). There remained a residue of 102 g, which was sub-sequently distilled in high vacuum (0.1 torr). The fraction yoing over at a temperature between 125 and 130C (i.e. 92 g) consisted of methyl glycerin.
Example 2 In an apparatus according to Example 1, 1 mole (91 g) of 3-chloro-2-methyl-propene-1 was mixed with 0.75 mole (35 g) of a 98% formic acid and 1.5 moles (128 g) of a 40% H2O2 were added at 60C in the course of 6 hours. Post-reaction: 4 hours at 60C. The mixture was catalytically freed from H2O2 and con-centrated by distillation - as described in Example 1. At a bottom temperature of 100C (12 torrs) a residue of 125 g remained and was subsequently subjected to total distillation at 12 torrs.
The fraction going over at a temperature between 103 and 107C
(i.e. 103 g) consisted of 3-chloro-2-methyl-propane diol-1,2.
Example 3 In an apparatus according to Example 1, 1 mole (70 g) of pentene-l was mixed with 1 mole of formic acid, 1.5 moles (128 g) of a 40% H2O2 were added with vapour cooling (approxi-mately 30C) in the course of 8 hours. After a post-reaction time of 8 hours the system had become single-phase. The system was catalytically freed from H2O2, neutralized with 90 g of a 40% NaOH and extracted four times, using 100 ml of ethyl acetate each time. The ethyl-acetate extracts were combined and freed from the solvent by distillation. A crude pentane-diol residue of 84 g was obtained. Its amount could be further increased in that the aqueous phase was concentrated to approximately one half and then again extracted thoroughly with ethyl acetate.
~21~3~-In the total distillation (12 torrs) 84 g of crude diol yielded an amount of 78 g of pure pentane-diol-1,2 which went over at 115 to 117C.
The test was repeated in a modified stirring apparatus which was provided Witil a pressure-maintaining valve after the reflux condenser. This valve opened at 2 atmospheres excess pressure. The hydroxylation of l-pentene could thus be carried out with the amounts specified above at a temperature of 50C.
Under these conditions bo-th the time for dosing in the H2O2 and the post-reaction time could be reduced to one half. The continu-ation of the test, which had been carried out at slightly increased pressure, produced practically the same yields as the pressure-less test.
Example 4 In an apparatus according to Example 1, 1 mole (84 g) of 2,3-dimethyl-butene-2 was mixed with 0.6 mole (28 g) of a 98%
formic acid and 1.5 moles (255 g) of a 20% H2O2 were added at 55C in the course of 4 hours. After a post-reaction time of
Examples of these substances are 2,4,4-trimethyl pentene-2, 1,2-di-(tert. butyl)-ethylene and decene-5. The monoolefins containirg 8 to 10 carbon atoms can also be substituted by 1 to 2 hydroxyl groups as in 2-ethyl hexen-2-ol-1. Finally according to the process of the invention straight-chain or branched diolefins containing 4 to 10 carbon atoms such as butadiene, isoprene, hexadiene-1,5 and decadiene-l,9 can be reacted to the corresponding tetrols.
The process according to the invention is preferably carried out at standard pressure. ~owever, since the reaction temperature should not be lower than 30C in order to obtain an acceptable rate of reaction, it is obvious that for olefins having a boiling point lower than 30C, the use of excess pressure is required. In this case it is expedient to so select the reac-tion temperature that the pressure does not exceed 10 bars.
Despite the mild reaction conditions the reactions according to the process of the invention surprisingly are very smooth and result in high yields of the desired diols, triols or -tetrols within reasonable reaction times.
~ hen carrying out the reaction in practice preferably the entire formic acid to be used is used together with the olefin as the starting material and the hydroyen peroxide is slowly added portionwise. However, it is also possible to start with a portion, for example, approximately one third of the total amount of the olefin to be hydroxylated, together wlth the total amount of formic acid and to add slowly, portionwise -the hydro-gen peroxide and the residual amount of the olefin to be hydroxy-Iated. The reaction mixture is stirred intensively. An adequate post-reaction time after combining all the reactants in the reactor is recommended in order to improve the reaction rate.
After the reaction has been completed the reaction products usually are present in the aqueous yhase in -the dissolved form. For many purposes these aqueous solutions can be further used directly. However, noi only has the residual content of hydrogen peroxide an adverse effect in most cases but it is also desirable to isolate, in a purer form, the diols, triols or tetrols obtained. Various measures are then suitable for the further treatment.
If a second phase separates from the reaction mixture, then a phase separation can be carried out. In many cases it is then advisable to decompose, to a grea-t extent, the hydrogen peroxide, which is contained substantially only in the aqueous phase. The decomposition can be brought about by allowing the mixture to stand for a lengthy period at elevated temperature (digestion) or by the action of a suitable catalyst (for example by passing over a supported platinum fixed bed catalyst) or by a combination of these two measures.
The reaction mixture then is expediently neutralized 3~
and extracted with a suitable solvent, for example, ethyl acetate. The solvent is distilled from the extract and, if required, the residue of crude diol, -triol or tetrol is freed from water still contained therein by heating under reduced pressure. As an alternative, the neutralization of the formic acid contained in the reaction mixture can be dispensed with.
In that case it is expedient either to carry out the thickening operation continuously in the manner of a distillation with steam and to continue it until the distillate contains only small amounts of formic acid or the formic acid is separated discon-tinuously in sucll a way that after separating the bulk of formic acid the residue is once more mixed with water, thickened again, repeating this operation several times. The residue of crude diol, triol or tetrol can then be freed from the volatile com-ponents still contained therein by heating under reduced pressure.
The crude diols, triols or tetrols thus obtained have degrees of purity of approximately 88 to 96%. If ~urther purifica-tion is required, then this can be carried out in the usual manner by recrystallization or by fractional distillation under reduced pressure.
The process according to the invention will be further described with reference to the following Examples in which, unless otherwise stated, data in percent relate to percent by weight in all the cases.
Example 1 1 mole (72 g) of crotyl alcohol was mixed with 0.5 mole (23 g) of a 98% formic acid and 1.5 moles (340 g) of a 15%
H2O2 in a stirring apparatus, with a reflux condenser mounted thereon, and stirred for 8 hours at 60C. The system was single-phase and contained 3.9% of H2O2. The mix-ture was passed over an NW 40 column of 30 cm length. The column was filled with 100 ml of fixed-bed catalyst (0.1% of platinum on Berl saddles).
3~
After passing through H2O2 could no longer be detected analyti-cally.
The mixture was then boiled for 2 hours with reflux and concentrated in vacuo (bottom temperature up to 100C at 12 torrs). There remained a residue of 102 g, which was sub-sequently distilled in high vacuum (0.1 torr). The fraction yoing over at a temperature between 125 and 130C (i.e. 92 g) consisted of methyl glycerin.
Example 2 In an apparatus according to Example 1, 1 mole (91 g) of 3-chloro-2-methyl-propene-1 was mixed with 0.75 mole (35 g) of a 98% formic acid and 1.5 moles (128 g) of a 40% H2O2 were added at 60C in the course of 6 hours. Post-reaction: 4 hours at 60C. The mixture was catalytically freed from H2O2 and con-centrated by distillation - as described in Example 1. At a bottom temperature of 100C (12 torrs) a residue of 125 g remained and was subsequently subjected to total distillation at 12 torrs.
The fraction going over at a temperature between 103 and 107C
(i.e. 103 g) consisted of 3-chloro-2-methyl-propane diol-1,2.
Example 3 In an apparatus according to Example 1, 1 mole (70 g) of pentene-l was mixed with 1 mole of formic acid, 1.5 moles (128 g) of a 40% H2O2 were added with vapour cooling (approxi-mately 30C) in the course of 8 hours. After a post-reaction time of 8 hours the system had become single-phase. The system was catalytically freed from H2O2, neutralized with 90 g of a 40% NaOH and extracted four times, using 100 ml of ethyl acetate each time. The ethyl-acetate extracts were combined and freed from the solvent by distillation. A crude pentane-diol residue of 84 g was obtained. Its amount could be further increased in that the aqueous phase was concentrated to approximately one half and then again extracted thoroughly with ethyl acetate.
~21~3~-In the total distillation (12 torrs) 84 g of crude diol yielded an amount of 78 g of pure pentane-diol-1,2 which went over at 115 to 117C.
The test was repeated in a modified stirring apparatus which was provided Witil a pressure-maintaining valve after the reflux condenser. This valve opened at 2 atmospheres excess pressure. The hydroxylation of l-pentene could thus be carried out with the amounts specified above at a temperature of 50C.
Under these conditions bo-th the time for dosing in the H2O2 and the post-reaction time could be reduced to one half. The continu-ation of the test, which had been carried out at slightly increased pressure, produced practically the same yields as the pressure-less test.
Example 4 In an apparatus according to Example 1, 1 mole (84 g) of 2,3-dimethyl-butene-2 was mixed with 0.6 mole (28 g) of a 98%
formic acid and 1.5 moles (255 g) of a 20% H2O2 were added at 55C in the course of 4 hours. After a post-reaction time of
4 hours the system had become single-phase. However, 4.2 g of olef;n could be removed by distillation (reaction rate = 95%).
After the usual catalytic H2O2 decomposition the mix~
ture was neutralized with 50 g of a 25% NaOH and extracted four times consecutively, using 100 ml of ethyl acetate each time.
The remaining aqueous phase was concentrated to one half by distillation and again extracted four times, using 50 ml of ethyl acetate each time. All the ethyl acetates were combined and freed from water, which still was in solution by azeotropic distillation. After distilling off the low-boiling component a bottom product (98 g, m.p. = 38 to 41C) remained. It had a diol content (pinacol) of 98go (yield 87%).
Example 5 In an apparatus according to Example 1, 1 mole (98 g) 3 ~
of heptene-3 was mixed with 1 mole (47 g) of a 98% formic acid.
In the course of 5 hours 1.5 moles (146 g) of a 35% H2O2 were added at 55C. Even after stirring for 2 hours at 60C the mixture remained two-phase. The mixture was catalytically freed from residual H2O2 and neutralized with 85 g of a 40% NaOH.
The aqueous phase was extracted four times with ethyl acetate, using 100 ml each time. It was -then concentrated to one half and again extracted twice with ethyl acetate. All the ethyl acetate extracts were combined with the organic phase and freed from the low-boiling components by distillation. A bottom pro-duct (crude heptane-diol-3,4 = 132 g) remained. It was con-verted by purifying fractionation (b.p.l2 = 111 to 113C) into the pure heptane-diol-1,3 in a yield of 86%.
Example 6 In an apparatus according to Example 1, 1 mole (129 g) of 2-ethyl-hexen-2-ol-1 was mixed with 0.7 mole (33 g) of a 98%
formic acid and in the course of 4 hours 1.5 mole (255 g) of a 20% H2O2 were added at 55C. The mixture was then stirred for a further 4 hours at 60C and still remained two-phase. The aqueous phase was separated and the organic phase was washed twice with water (50 ml each tim~).
All the combined aqueous phases were catalytically freed from H2O2 and neutralized with 65 g of 40% NaOH. The aqueous phase was then thoroughly extracted with ethyl acetate.
The ethyl-acetate extract was combined with the organic phase and freed from the low-boiling components by distillation. The remaining bottom product weighed 143y and could be converted by high-vacuum distillation (0.1 torr, 90 to 92C) into pure 2-ethyl hexane-triol-1,2,3.
3~
After the usual catalytic H2O2 decomposition the mix~
ture was neutralized with 50 g of a 25% NaOH and extracted four times consecutively, using 100 ml of ethyl acetate each time.
The remaining aqueous phase was concentrated to one half by distillation and again extracted four times, using 50 ml of ethyl acetate each time. All the ethyl acetates were combined and freed from water, which still was in solution by azeotropic distillation. After distilling off the low-boiling component a bottom product (98 g, m.p. = 38 to 41C) remained. It had a diol content (pinacol) of 98go (yield 87%).
Example 5 In an apparatus according to Example 1, 1 mole (98 g) 3 ~
of heptene-3 was mixed with 1 mole (47 g) of a 98% formic acid.
In the course of 5 hours 1.5 moles (146 g) of a 35% H2O2 were added at 55C. Even after stirring for 2 hours at 60C the mixture remained two-phase. The mixture was catalytically freed from residual H2O2 and neutralized with 85 g of a 40% NaOH.
The aqueous phase was extracted four times with ethyl acetate, using 100 ml each time. It was -then concentrated to one half and again extracted twice with ethyl acetate. All the ethyl acetate extracts were combined with the organic phase and freed from the low-boiling components by distillation. A bottom pro-duct (crude heptane-diol-3,4 = 132 g) remained. It was con-verted by purifying fractionation (b.p.l2 = 111 to 113C) into the pure heptane-diol-1,3 in a yield of 86%.
Example 6 In an apparatus according to Example 1, 1 mole (129 g) of 2-ethyl-hexen-2-ol-1 was mixed with 0.7 mole (33 g) of a 98%
formic acid and in the course of 4 hours 1.5 mole (255 g) of a 20% H2O2 were added at 55C. The mixture was then stirred for a further 4 hours at 60C and still remained two-phase. The aqueous phase was separated and the organic phase was washed twice with water (50 ml each tim~).
All the combined aqueous phases were catalytically freed from H2O2 and neutralized with 65 g of 40% NaOH. The aqueous phase was then thoroughly extracted with ethyl acetate.
The ethyl-acetate extract was combined with the organic phase and freed from the low-boiling components by distillation. The remaining bottom product weighed 143y and could be converted by high-vacuum distillation (0.1 torr, 90 to 92C) into pure 2-ethyl hexane-triol-1,2,3.
3~
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for hydroxylating an olefin selected from 3-chloro-2-methyl-propene-1, straight-chain or branched mono-olefins, which are either unsubstituted or substituted by 1 to 2 hydroxyl groups and contain 4 to 7 carbon atoms and a terminal or internal double bond, straight-chain or branched monoolefins, which are either unsubstituted or substituted by 1 or 2 hydroxyl groups and contain 8 to 10 carbon atoms and an internal double bond and straight-chain or branched diolefins containing 4 to 10 carbon atoms, in which the olefin to be hydroxylated is reacted at temperature between 30 and 80°C with less than 2 moles of formic acid and less than 2 moles of hydrogen peroxide per mole of double bond to be hydroxylated, formic acid is present in a concentration between 20 and 100 percent by weight and hydrogen peroxide is present in a concentration of less than 50 percent by weight and that the concentration of the hydrogen peroxide in the aqueous phase of the reaction mixture is kept below 15 percent by weight during the entire reaction.
2. A process according to claim 1 in which the reac-tion is carried out at a temperature between 45 and 60°C.
3. A process according to claim 1 in which the formic acid is present in an amount of 0.2 to 0.8 mole per mole of double bond to be hydroxylated.
4. A process according to claim 1, 2 or 3 characterized in that the hydrogen peroxide is present in an amount of 1.1 to 1.5 moles per mole of double bond to be hydroxylated.
5. A process according to claim 1, 2 or 3 in which the hydrogen peroxide is present in a concentration of 15 to 40 per-cent by weight.
6. A process according to claim 1, 2 or 3 in which the olefin is selected from butene-1, butene-2, pentene-1, hexene-1, heptene 1 and heptene-3.
7. A process as claimed in claim 1, 2 or 3 in which the olefin is selected from 2-methyl-propene-1, 3-methyl-butene-1, 3,3-dimethyl-butene-1, 2,3-dimethylbutene-1, 2,3-dimethyl-butene-2, 2-methyl pentene-1, 2-methyl pentene-2, 3-methyl pentene-2 and 2-ethyl butene-1.
8. A process as claimed in claim 1, 2 or 3 in which the olefin is selected from buten-1-ol-3, buten-2-ol-1 (crotyl alchol), butene-2-diol-1,4, 3-methyl buten-3-ol-1, 3-methyl buten-2-ol-1 and 2-methyl-buten-3-ol-2.
9. A process as claimed in claim 1, 2 or 3 in which the olefin is selected from 2,4,4-trimethyl pentene-2, 1,2-di-(tert. butyl)-ethylene and decene-5.
10. A process as claimed in claim 1, 2 or 3 in which the olefin is selected from butadiene, isoprene, hexadiene-1,5 and decadiene-1,9.
11. A process as claimed in claim 1, 2 or 3 in which the olefin is 2-ethyl hexen-2-ol-1.
12. A process as claimed in claim 1, 2 or 3 in which the olefin is 3-chloro-methyl-propene-1.
13. A process as claimed in claim 1, 2 or 3 effected at standard pressure.
14. A process as claimed in claim 1, 2 or 3 in which the olefin has a boiling point lower than 30°C and excess pres-sure up to 10 bars is used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2937840A DE2937840C2 (en) | 1979-09-19 | 1979-09-19 | Process for the production of diols, triols or tetrols by hydroxylation of aliphatic mono- or diolefins |
| DEP2937840.3-42 | 1979-09-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1218385A true CA1218385A (en) | 1987-02-24 |
Family
ID=6081259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000360664A Expired CA1218385A (en) | 1979-09-19 | 1980-09-19 | Process for hydroxylating short-chain aliphatic mono- or di-olefins |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0025890B1 (en) |
| JP (1) | JPS5936966B2 (en) |
| AT (1) | ATE3027T1 (en) |
| AU (1) | AU6025180A (en) |
| BR (1) | BR8005948A (en) |
| CA (1) | CA1218385A (en) |
| DE (1) | DE2937840C2 (en) |
| ES (1) | ES8104167A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2145076A (en) * | 1983-08-13 | 1985-03-20 | Ciba Geigy Ag | A process for producing 1,2-alkanediols |
| JPS6045540A (en) * | 1983-08-22 | 1985-03-12 | T Hasegawa Co Ltd | Ethylene glycol derivative |
| US4479021A (en) * | 1983-08-30 | 1984-10-23 | Ciba-Geigy Corporation | Continuous process for producing 1,2-alkanediols |
| DE3442937C2 (en) * | 1984-11-24 | 1986-11-06 | Degussa Ag, 6000 Frankfurt | Process for the continuous production of 1,2-pentanediol |
| DE19743015A1 (en) * | 1997-09-29 | 1999-04-01 | Basf Ag | Process for the preparation of vicinal diols or polyols |
| DE102004060541A1 (en) | 2004-12-15 | 2006-06-29 | Degussa Ag | Process for the preparation of alkanediols and alkanetriols having a vicinal diol group |
| DE102013203420A1 (en) | 2013-02-28 | 2014-08-28 | Evonik Industries Ag | Hydrogenolysis of furfuryl alcohol to 1,2-pentanediol |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB634118A (en) * | 1942-02-09 | 1950-03-15 | Bataafsche Petroleum | A process for the catalytic hydroxylation of olefinic compounds |
| US2492201A (en) * | 1946-06-07 | 1949-12-27 | Swern Daniel | Hydroxylation process |
| FR1047126A (en) * | 1951-12-27 | 1953-12-11 | Gustave Maubec Ets | Preparation of low acid number fatty polyols |
| DE956505C (en) * | 1953-01-18 | 1957-01-17 | Ruhrchemie Ag | Process for the production of tricyclo- (5, 2, 1, 0) -dekantriol- (3, 4, 8) or - (3, 4, 9) |
| GB1119612A (en) * | 1966-04-20 | 1968-07-10 | W J Bush & Company Ltd | Hydroxylation of alkenyl substituted aromatic compounds |
-
1979
- 1979-09-19 DE DE2937840A patent/DE2937840C2/en not_active Expired
-
1980
- 1980-07-09 AU AU60251/80A patent/AU6025180A/en not_active Abandoned
- 1980-07-09 ES ES493223A patent/ES8104167A1/en not_active Expired
- 1980-08-28 AT AT80105116T patent/ATE3027T1/en not_active IP Right Cessation
- 1980-08-28 EP EP80105116A patent/EP0025890B1/en not_active Expired
- 1980-09-17 BR BR8005948A patent/BR8005948A/en unknown
- 1980-09-17 JP JP55128070A patent/JPS5936966B2/en not_active Expired
- 1980-09-19 CA CA000360664A patent/CA1218385A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES493223A0 (en) | 1981-04-16 |
| JPS5936966B2 (en) | 1984-09-06 |
| ATE3027T1 (en) | 1983-04-15 |
| JPS5653627A (en) | 1981-05-13 |
| AU6025180A (en) | 1981-03-26 |
| DE2937840A1 (en) | 1981-04-02 |
| ES8104167A1 (en) | 1981-04-16 |
| DE2937840C2 (en) | 1985-03-28 |
| EP0025890A1 (en) | 1981-04-01 |
| BR8005948A (en) | 1981-03-31 |
| EP0025890B1 (en) | 1983-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4918244A (en) | Preparation of MTBE from TBA and methanol | |
| US2967873A (en) | Process for the production of aliphatic and cycloaliphatic monocarboxylic acid alkyl esters | |
| US4331824A (en) | Process for preparation of high purity isobutylene | |
| CA1218385A (en) | Process for hydroxylating short-chain aliphatic mono- or di-olefins | |
| US4925989A (en) | MTBE preparation from isobutylene/TBA and methanol in presence of an acid resin catalyst | |
| US4256913A (en) | Preparation of carboxylic acids using a BF3 catalyst complex | |
| US4175210A (en) | Etherification process | |
| GB1594158A (en) | Purification of methyl tert-butyl ether | |
| US4351970A (en) | Method of preparing alcohols having two to four carbon atoms by catalytic hydration of olefins | |
| US2122812A (en) | Hydrogenation of unsaturated ethers and esters | |
| Eguchi et al. | The Mechanism of Ethylenimine Formation by the Action of Grignard Reagents on Ketoximes | |
| US3895076A (en) | Process for the preparation of monomethylethers of dihydroxybenzene | |
| JPS5942659B2 (en) | Hydroxylation method of cyclic olefin having 1 or 2 double bonds | |
| US4337363A (en) | Process for the preparation of 3-(4-methyl-3-cyclohexen-1-yl) butyraldehyde | |
| DE2635566C3 (en) | Process for the preparation of oxirane compounds by cracking a corresponding alkylene glycol monoester | |
| US3825601A (en) | Hydroformylation of internal olefins | |
| US3959394A (en) | Process for selective methylation of phenols | |
| US3325245A (en) | Lithium phosphate catalyst | |
| CA1138898A (en) | Phenylethyl alcohol preparation with mixed feeds | |
| US3491148A (en) | Production of amines from mixtures containing n-amyl alcohol and cyclopentanol | |
| US3205244A (en) | Improved catalytic synthesis of carboxylic acids from olefins, carbon monoxide and water | |
| US3080371A (en) | Process for the production of | |
| US3318955A (en) | Production of formaldehyde | |
| US3956407A (en) | Alkenol production | |
| EP0226242B1 (en) | Downflow isomerization of epoxides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |